Supelco Ionic Liquid GC Columns. Introduction to the Technology

Transcription

1 This presentation describes what Supelco ionic liquid GC columns are, and includes several column selection charts. 1

2 Overview 2

3 Selectivity is important as it has the greatest influence on resolution; greater than either capacity or efficiency. Selectivity is governed by two aspects of interaction mechanisms: Which mechanisms are available The relative strengths of these mechanisms to each other Interaction mechanisms are dictated by the base structure of the stationary phase, as well as any pendent groups. With a few exceptions (namely chiral and PLOT columns), just three base structures are typically used as GC stationary phases. Substituted polysiloxane polymers, the origin of which can be traced back to 1952 and the very birth of the GC technique Polyethylene glycols, introduced ~1956 Ionic liquids, a new GC stationary phase platform introduced in

4 The most widely used GC phase platforms are based on polysiloxane polymers or polyethylene glycols. While some improvements have occurred, these phase platforms have remained virtually unchanged nearly as long as GC has existed. Drawbacks include: Active hydroxyl (-OH) groups at the polymer termini make these phases susceptible to a back-biting reaction if exposed to moisture and oxygen, leading to phase degradation and contributing to column bleed The limited ability to modify the phase limits the ability to alter selectivity A major limitation of PEG phases is their thermal limit of around 280 ºC 4

5 Ionic liquids consist of two or more organic cations, joined by a linkage, and associated with anions, which can be either inorganic or organic. Ionic liquids differ physically and chemically from other phases. They are much smaller compared to big, bulky polysiloxane polymer and polyethylene glycol phases, plus there are no active hydroxyl groups. These features lead to greater stability, even in the presence of moisture and/or oxygen. Many modifications are possible to make columns with unique selectivity. The base structure can be dicationic or polycationic There are numerous cation, linkage, and anion choices Pendant groups can be added to cations and/or linkages 5

6 GC Column Polarity Scale 6

7 Our GC column polarity scale is a convenient tool to classify ionic liquid GC columns against each other, and also against non-ionic liquid GC columns. The procedure we follow was proposed to us by Prof. Luigi Mondello (University of Messina, Italy). Each column is characterized with a series of five probes plus several n-alkane markers to determine the retention index for each probe. McReynolds Constants are then calculated using the retention index data of the column relative to the retention index data for the same five probes on squalane, the most non-polar GC stationary phase. The five McReynolds Constants are summed to obtain Polarity (P) values, which are then normalized to SLB-IL100 (set at P=100) to obtain Polarity Number (P.N.) values. Our GC column polarity scale can be used for column selection because it allows multiple columns to be compared easily, because all P.N. values are relative to both squalane (0 on the scale) and SLB-IL100 (100 on the scale). 7

8 McReynolds Constants, Polarity (P) values, and Polarity Number (P.N.) values for several ionic liquid and non-ionic liquid columns are shown. 8

9 The GC Column Polarity Scale illustrates the relative polarities of various column phases to one another. To the left of the scale are the positions and maximum temperatures of several non-ionic liquid columns. To the right of the scale are the positions and maximum temperatures of current Supelco ionic liquid columns. We expect ionic liquid columns will be introduced into the intermediate polar region. The scale is divided into five regions: The first four regions are generally accepted and used by several GC column manufacturers The fifth region (extremely polar) was required with the introduction of the ionic liquid column SLB-IL111 in 2010, because no column existed within this polarity region before Note that there are several gaps to the left of the scale. These are attributed to the limited modifications possible with polysiloxane polymer and polyethylene glycol phases. 9

10 Temperature Effects on Selectivity 10

11 A visual example of this temperature effect phenomenon is shown using a simple analyte list comprised of one alkane (n-tridecane) and four aromatics (toluene, ethylbenzene, p-xylene, and isopropylbenzene) on the SLB-IL100. Three runs are shown, each using a different isothermal oven temperature. All other conditions remain constant. A higher oven temperature results in the decreased retention of all analytes. This is expected because a higher oven temperature will weaken all stationary phase-analyte interactions. But what about selectivity? A higher oven temperature results in a selectivity change. Why? Let s first identify the stationary phase-analyte interactions at work here. Alkanes (such as n-tridecane, peak 5) are primarily retained by dispersive interactions, whereas aromatics are retained by dipole and induced dipole interactions in addition to dispersive interactions. As mentioned above, a higher temperature will weaken all stationary phaseanalyte interactions. However, all interactions do not weaken at the same rate. The alkane loses retention quicker than the aromatics because the dispersive interactions used for its retention weaken quicker with a higher oven temperature than the dipole and induced dipole interactions used for part of the retention of the aromatics. 11

12 Can we manipulate oven temperature to optimize a separation? We can try. This temperature effect is exhibited by all columns (ionic liquid and non-ionic liquid). The greater the polarity of the column, the more pronounced the effect. Highly polar and extremely polar columns fully demonstrate this effect. Intermediate polar and polar columns show this effect to a much lesser degree. Non-polar columns rarely demonstrate this effect. Oven temperature and/or ramp rate can both be adjusted. Want to optimize a separation? Try slight oven temperature changes (10 ºC up or down), or slight ramp rate changes (5 ºC/min faster or slower). Need to duplicate a published chromatogram? Use the identical oven temperatures and ramp rates. 12

13 Column Selection 13

14 Ionic liquid GC columns are relatively new. They were introduced in Compare this to the 1950 s when polysiloxane polymers and polyethylene glycols were introduced. Not all suitable applications that ionic liquid columns can perform are yet discovered. The following charts serve as a starting point. Chromatograms for some applications can be found in the Supelco Ionic Liquid GC Columns Applications presentation. 14

15 Chromatograms for some applications can be found in the Supelco Ionic Liquid GC Columns Applications presentation. 15

16 Chromatograms for some applications can be found in the Supelco Ionic Liquid GC Columns Applications presentation. 16

17 Chromatograms for some applications can be found in the Supelco Ionic Liquid GC Columns Applications presentation. 17

18 SLB-IL59 Application: Selectivity more polar than PEG/wax phases, resulting in unique elution patterns. Higher maximum temperature than PEG/wax columns (300 ºC compared to ºC). Great choice for analysis of neutral and moderately basic analytes. Launched in Phase: Non-bonded; 1,12-Di(tripropylphosphonium)dodecane bis(trifluoromethylsulfonyl)imide Temp. Limits: Subambient to 300 ºC (isothermal or programmed) 18

19 SLB-IL60 Application: Modified (deactivated) version of SLB-IL59 provides better inertness. Selectivity more polar than PEG/wax phases, resulting in unique elution patterns. Higher maximum temperature than PEG/wax columns (300 ºC compared to ºC). Excellent alternative to existing PEG/wax columns. Also a good GCxGC column choice. Launched in Phase: Non-bonded; 1,12-Di(tripropylphosphonium)dodecane bis(trifluoromethylsulfonyl)imide Temp. Limits: 35 ºC to 300 ºC (isothermal or programmed) 19

20 SLB-IL61 Application: The first of our third generation ionic liquid columns. Modified (triflate anion) version of SLB-IL59 increases inertness. Selectivity more polar than PEG/wax phases, resulting in unique elution patterns. Higher maximum temperature than PEG/wax columns (290 ºC compared to ºC). Great choice for analysis of neutral and moderately basic analytes. Launched in Phase: Non-bonded; 1,12-Di(tripropylphosphonium)dodecane bis(trifluoromethylsulfonyl)imide trifluoromethylsulfonate Temp. Limits: 40 ºC to 290 ºC (isothermal or programmed) 20

21 SLB-IL76 Application: The first of our second generation ionic liquid columns. Phase structure engineered with numerous interaction mechanisms, resulting in selectivity differences even when compared to columns with similar GC column polarity scale values. Launched in Phase: Non-bonded; Tri(tripropylphosphoniumhexanamido)triethylamine bis(trifluoromethylsulfonyl)imide Temp. Limits: Subambient to 270 ºC (isothermal or programmed) 21

22 SLB-IL82 Application: Selectivity slightly more polar than polysiloxane phases with a high percentage of cyanopropyl pendent groups, resulting in unique elution patterns. Great choice for analysis of neutral and moderately basic analytes. Launched in Phase: Non-bonded; 1,12-Di(2,3-dimethylimidazolium)dodecane bis(trifluoromethylsulfonyl)imide Temp. Limits: 50 ºC to 270 ºC (isothermal or programmed) 22

23 SLB-IL100 Application: World s first commercially available ionic liquid GC column. Serves as the benchmark of 100 on our GC column polarity scale. Selectivity almost identical to TCEP phase. Higher maximum temperature than TCEP columns (230 ºC compared to 140 ºC). Great choice for analysis of neutral and polarizable (contain double and/or triple C-C bonds) analytes. Launched in Phase: Non-bonded; 1,9-Di(3-vinylimidazolium)nonane bis(trifluoromethylsulfonyl)imide Temp. Limits: Subambient to 230 ºC (isothermal or programmed) 23

24 SLB-IL111 Application: World s first commercial column to rate over 100 on our GC column polarity scale. Selectivity most orthogonal to non-polar and intermediate polar phases, resulting in very unique elution patterns. Maximum temperature of 270 ºC is very impressive for such an extremely polar column. Great choice for separation of polarizable analytes (contain double and/or triple C-C bonds) from neutral analytes. Also a good GCxGC column choice. Launched in Phase: Non-bonded; 1,5-Di(2,3-dimethylimidazolium)pentane bis(trifluoromethylsulfonyl)imide Temp. Limits: 50 ºC to 270 ºC (isothermal or programmed) 24

25 Summary / Related Products / Resources 25

26 Ionic liquids are something totally new and completely different in the world of GC phases. They have the opportunity to impact current GC and GC-MS practices along several paths: Columns can be engineered with identical selectivity to non-ionic liquid columns but with higher operating temperatures and less susceptibility to damage from moisture and/or oxygen Columns can be engineered with completely unique selectivity to nonionic liquid columns producing good peak shape and resolution for compounds of varying functionality Columns can be used in multidimensional separations due to their engineered orthogonality and high thermal stability A wide range of interaction mechanisms translates to different selectivity options. 26

27 There are multiple related products. Most of them are touched on in the 28- page, 4-color Maximize Performance! brochure. This piece lists all the common replacement items, including septa, liners, ferrules, solvents, syringes, vials, purifiers, and much more for several GC makes/models, including Agilent/HP, PerkinElmer, Shimadzu, Thermo, and Varian. This must-have brochure can be downloaded from <sigma-aldrich.com/gclearning>. 27

28 There are two complementary pieces. The first is the Applications presentation. It includes multiple chromatograms across many industry types. Analyte IDs and GC conditions are included in the speaker notes for most. The second is a Bibliography of peer-reviewed journal articles leading up to and beyond the seminal 2005 JACS (Journal of the American Chemical Society) article. It is updated periodically. Both pieces can be downloaded from <sigma-aldrich.com/il-gc-lit>. 28

29 Contacts are as follows: Marketing for GC Columns is Mike Buchanan Marketing for GC Accessories and Gas Purification is Jaime Martain Technical is Len Sidisky An Ionic Liquid GC Columns brochure is planned. Use the Maximize Performance! brochure for related products. Visit our ionic liquid landing page to find: Detailed product information In-depth technical literature and applications notes A bibliography of journal articles featuring ionic liquid columns A form to request an evaluation column 29

30 Thank You 30